1,2-dithiolones having sulphur-containing substituents

ABSTRACT

1,2-DITHIOL-3-ONES HAVING SUBSTITUENTS WHICH COMPRISES CERTAIN ORGANIC RADICALS BONDED TO THE 5-POSITION OF THE DITHIOLONE NUCLEUS VIA A SULPHUR ATOM WHICH MAY BE MONP- OR DIOXIDIZED, WHICH ARE OF EXCELLENT MICROBICIDAL ACTIVITY ESPECIALLY AGAINST FUNGI AND BACTERIA; A NOVEL PROCESS FOR THE PRODUCTION OF THOSE OF THE NEW COMPOUNDS IN WHICH THE BRIDGE IS A SULPHUR OR MONO-OXIDIZED SULPHUR BRIDGE; METHODS OF INHIBITING MICROBIAL GROWTH WITH THE AID OF THE NOVEL COMPOUNDS. AND ANTIMICROBIAL COMPOSITIONS CONTAINING THE LATTER AS ACTIVE INGREDIENTS.

US. Cl. 260-327 C 23 Claims ABSTRACT OF THE DISCLOSURE1,2-dithiol-3-ones having substituents which comprise certain organicradicals bonded to the -position of the dithiolone nucleus via a sulphuratom which may be monoor dioxidized, which are of excellent microbicidalactivity especially against fungi and bacteria; a novel process for theproduction of those of the new compounds in which the bridge is asulphur or mono-oxidized sulphur bridge; methods of inhibiting microbialgrowth with the aid of the novel compounds, and antimicrobialcompositions containing the latter as active ingredients.

CROSS REFERENCE TO RELATED APPLICATIONS This application is a divisionof application Ser. No. 643,359, filed June 5, 1967, now U.S. Pat. No.3,546,235, which in turn is a continuation-in-part of application Ser.No. 555,994, filed June 8, 1966, now abandoned.

BACKGROUND OF THE INVENTION Field of the invention The present inventionconcerns new sulphur-containing 1,2-dithiol-3-ones which comprises inthe 5-position substituents which are bonded thereto via a sulphur atom,an SO or an -SO bridge (i.e., 1,2-dithiol- 3-one-5-sulphides,-5-sulphoxides and -5-sulphones) and have microbicidal properties,processes for the production of these compounds, compositions containingthem as active ingredients, and their use for the control ofmicroorganisms, particularly of fungi and bacteria, in the protection ofplants and materials.

Description of the prior art It is known from the literature that thering system of 1,2-dithio1-3-one can easily be disrupted by nucleophilicreactants, particularly in a strongly alkaline medium (cf. F. Boberg,Liebigs Annalen der Chemie, 666, 88 [1963]; 679, 118 [1964]; AngewandteChemie 73, 579 [1961]; 74, 495 [1962]; 76, 575 [1964]. An exchange ofthe chlorine atom in the 5-position in 5-chloro-l,2-dithiol-3- ones foranother substituent whilst maintaining the ring system has only beendescribed up to the present for the radicals of certain organic amines.In this known exchange reaction generally a great part of the S-chloro-1,2-dithiol-3-one used is decomposed by rupture of the ring [R Bobergand A. Marei, Liebigs Ann. Chem. 666, 88 (1963); F. Boberg, Liebigs Ann.Chem. 681, 169 (1965)].

SUMMARY OF THE INVENTION It has now been found that, surprisingly,5-halogen- United States Patent O case of strongly acid thiols theiralkali metal, alkaline earth metal or ammonium salts, or with thiones orwith salts of sulphinic acids which are nucleophilic reactants. In thereaction, the halogen atom in the 5-position is exchanged without theheterocyclic ring system being disrupted, and new 1,2-dithiol-3-onessubstituted in the 5-position via an S atom or -S0 group, or, afteroxidation of the S atom, an -SO- or -SO;- group are obtained which areof the formula 1L1 (1) In this formula:

Y represents sulphur or the sulphinyl or sulphonyl group,

R represents a halogen atom having an atomic number of at most 35, alower alkyl radical or an unsubstituted or substituted phenyl radical,

R represents an unsubstituted or substituted aliphatic hydrocarbonradical, or a carbocyclic or heterocyclic radical which is preferablymononuelear, or an unsubstituted or substituted preferably mononuclearcarbocyclic or heterocyclic radical fused with an unsubstituted orsubstituted benzene nucleus, and when Y is sulphur, also the groupwherein Q represents the amino group or a substituted amino group, thepyrrolidino, piperidino, morpholino or hexamethylenimino radical, analkoxy radical or an unsubstituted or substituted lower aliphatichydrocarbon radical, and -E represents oxygen, sulphur, the imino groupor an alkylated imino group, with the proviso that when R represents anunsubstituted or substituted phenyl radical, R represents anunsubstituted or substituted aliphatic hydrocarbon radical.

Because of their excellent antimicrobial properties, expecially theirfungicidal, fungistatic, bactericidal and bacteriostatic properties, thenew sulphur-containing 1,2- dithiol-3-ones of the general Formula I aresuitable for combatting phytopathogenic fungi on plants, and fungi andbacteria which damage and destroy organic materials and useful objects,as well as: for the protection of plants against attack by fungi. Thenew active substances can also be used for soil disinfection. Theirtoxicity for warm-blooded animals is remarkably low.

The new compounds also act as systemic fungicides. Because of theseproperties, plants treated with the new 1,2-dithiol-3-ones are givenwider and longer-lasting protection from attack by fungi. The new activesubstances can also be used for the treatment of seeds withoutgermination being aflfected. For use in plant protection, the new activesubstances are made into compositions with distributing agents and/orcarriers in the usual way and applied to the plants in concentrations ofactive substance within the range of 0.01 and 10% by weight calculatedon the weight of the composition.

In addition the new compounds of general Formula I are also suitable forcombating microorganisms which damage and destroy organic materials andcan thus be used for the protection of such materials. Fungi andbacteria are meant by such microorganisms which attack, in particular,keratine materials, those containing cellulose (wood, fabrics, leather,etc.) synthetic materials and those which are applied by painting. Byimpregnating'with solutions or dispersions of active substances having acontent of active substance of at least 1 g./litre, the materials anduseful objects are given a good and long-lasting protection. For thispurpose, the active substances can also be used in combination withother substances suitable for the protection of material.

DETAILED DESCRIPTION OF THE INVENTION AND OF PREFERRED EMBODIMENTSTHEREOF According to the present invention, microbicidally active1,2-dithiol-3-one substituted in the 5-position by way of an S atoms oran --S or -SO group, are obtained by reacting aS-halogen-1,2-dithiol-3-one with hydrogen compounds of divalent sulphurin the presence of a solvent or diluent and, if desired, oxidising the-thioethers so obtained with an oxidising agent to form thecorresponding sulphinyl or sulphonyl compounds. The preferredS-halogen-1,2-dithiol-3-ones usable according to the invention are thosewhich contain chlorine or bromine in the 5-position and a substitutentwhich is inert under the reaction conditions in the 4-position. Examplesof the latter are halogen having an atomic number of at most 35 or anunsubstituted or substituted phenyl radical, whereby substituents ofthis radical must also be stable under the reaction conditions.

Both organic and also inorganic compounds having an SH- group or athiono group which can be converted into such can be used according tothe invention as hydrogen compounds of divalent sulphur. Such organiccompounds correspond to the formula R SH, wherein R represents anunsubstituted or substituted aliphatic, homocyclic or heterocyclicradical, those condensed with an unsubstituted or substituted benzenenucleus also being understood by homocyclic and heterocyclic radicals.In addition, R can represent the group wherein Q represents an alkoxyradical, an unsubstituted or substituted amino group, the pyrrolidino,piperidino, morpholino or hexamethylenimino radical, a substituted orunsubstituted lower aliphatic radical, and E represents oxygen, sulphur,the imino group or an alkylated imino group. Examples of compounds whichcontain such a grouping are organic monoand di-thiocarboxylic acids,organic dithiocarbamic acids and dithiocarbonic acid- O-esters, whichare to be used for the reaction, in particular, as salts, e.g., asammonium or alkali metal salts. Organic thiols or thiones which can beconverted into such can be used both as such as well as salts for theprocess according to the invention. Inorganic and organic compoundshaving an SH- group are, e.g., the thiosulphates and thiourea. Onreacting thiosulphates with a 5- halogen-1,2-dithiol-3-one, thecorresponding bis-[1,2-dithiol-3-on-5-yl] -sulphide is formed asreaction product.

As solvents or diluents for the process according to the invention,water, organic solvents such as aromatic hydrocarbons, chlorinatedaromatic and aliphatic hydrocarbons, alcohols, ketones, esters, ethers,amides, sulphoxides and mixtures of the solvents mentioned can be used.The reaction temperatures lie between 70 and 200 0., preferably between-40 and 120 C.

To attain good yields of 1,2-dithiol-3-on-5-yl sulphides, it isadvantageous to perform the process according to the invention in anacid to weakly alkaline reaction medium. In some cases, it is ofadvantage to perform the reaction in the presence of an acid bindingagent. Salts of weak acids such as carbonates, acetates, borates,phosphates; metal oxides such as magnesium oxide and zinc oxide;tertiary amines such as trialkylamines, mixtures of amines and salts ofamines can be used as acid binding agents. Acids such as acetic acid,phosphoric acid, etc. can be used to reduce the basicity of a stronglyalkaline reaction medium.

The thioethers of 1,2-dithol-3-ones obtained according to the process ofthe invention can be oxidised to form the corresponding sulphinylcompounds. The following oxidising agents, for example, can be used forthe oxidation of r 4 v the S-thio-derivatives: hydrogen peroxide,organic per acids such as peracetic acids, monoperphthalic acid,performic acid, perbenzoic acid, 3-chloro-perbenzoic acid,trifluoroperacetic acid, inorganic peracids, e.g., Caros acid,peroxydisulphuric acid and their salts. The per acids mentioned can beused for the reaction as such or they can be produced, however, at thesite of the reaction from hydrogen peroxide and the corresponding acids,optionally in the presence of a catalyst such as mineral acid. Ingeneral, the use of equimolar amounts of oxidising agent isadvantageous. If desired, the thio-derivatives of sulphinyl compoundscan be oxidised to form the sulphonyl compounds.

1,2-dithiol-3-one-5-thioethers of general Formual II wherein R has themeanings given in Formula I and R represents an unsubstituted orsubstituted aliphatic radical, a heterocyclic radical or a heterocyclicradical bound by way of an alkylene bridge, particularly a methylenebridge, can also be obtained by reacting a 1,2-dithiol-3-one of thegeneral Formula III X S S sash},

Iii (III) wherein R X and Q have the meanings given in Formula I, with acompound of general formula IV wherein R' has the meaning given inFormula II and Z represents a reactive halogen atom or an aliphaticsulphonyloxy radical.

S-thioethers of 1,2-dithiol-3-ones of the general Formula V wherein Rrepresents an unsubstituted or substituted phenyl radical, and

R represents an unsubstituted or substituted aliphatic radical,

may also be prepared by oxidising a S-thioether of a 1,2-dithiol-3-thione of the general Formula VI 1k 1 (VI) wherein R' and R"have the meanings given above with an oxidising agent to form thecorresponding compound of the general Formula V.

As oxidising agent can be used, for example, mercury- (lD-acetate orpotassium permanganate.

The reaction is performed in the presence of an inorganic solvent stableunder the reaction conditions such as acetone and chloroform and attemperatures ranging from 10 to 50 0., preferably from 0 to 25 C.

In general, the new 1,2-dithiol-3-ones of general Formula I arecrystalline compounds. If these new sulphur compounds have reactivesubstituents such as exchangeable halogen, or hydroxyl, amino, mercapto,carboxyl groups, etc., then the reactions usual for the correspondingfunction can be performed, e.g., etherification, esterification,saponification, alkylation, etc.

It is generally advantageous to use an equimolar amount of the oxidisingagent in the reaction with thioethers of 1,2-dithiolones falling underFormula 1.

Compounds falling under Formula I in which Y represents -SO are producedby oxidising a thioether of 1,2 -dithiol3-one, of the formula wherein Rhas the meaning given in Formula I, and X represents a halogen atom,

with a sulphinic acid salt of the formula (VIII) wherein R has themeaning given in Formula I, and

Z represents the equivalent of a metal atom cation preferably an alkalimetal or alkaline earth metal cation or the ammonium ion.

Iron, zinc or aluminum salts of Formula III can also be used.

When R in the compounds of Formula I is a halogen atom, chlorine is thepreferred halogen. A phenyl radical symbolised by R can containsubstituents which are inert under the reaction conditions, e.g.,halogen having an atomic weight of less than 100, or lower alkyl. Byaliphatic hydrocarbon radicals symbolised by R are meant straight andbranched chain alkyl and alkenyl radical having 1 to 20 carbon atoms;the optionally condensed homocyclic and heterocyclic radical can besaturated, partly unsaturated or aromatically unsaturated. Preferredexamples from this class are:

(a) Of aromatic homocycles, particularly the phenyl radical, also theradicals of naphthalene or tetraline which, optionally, can be bound byWay of a methylene group to Y, and

(b) of heterocycles, the 5- or 6-membered rings optionally bound to Y byway of an alkylene bridge, particularly a methylene bridge, which ringshave 1 to 3 hetero atoms, in particular nitrogen, oxygen or sulphuratoms, e.g., the radicals of the following heterocycles: furan,thiophene, pyridine, oxazole, thiazole, imidazole, 1,2-dithiol-3-one,oxadiazoles, thiadiazoles, triazines and also their partially andexhaustively hydrogenated derivatives and their derivatives containinga fused benzo radical, e.g., the benzoxazolyl or benzimidazolyl radical.

The radicals symbolised by R can have one or more substituents which areinert under the reaction conditions. Such substituents are, e.g., thefollowing:

Halogen, hydroxyl, acyloxy, alkylsulphonyloxy, amino, alkylamino,dialkylamino, cyano, carboxyl, carbamoyl, thiocarbamoyl, alkylcarbamoyl,dialkylcarbamoyl, benzylcarbamoyl, alkoxycarbonyl, alkoxyalkoxycarbonyl,halogenalkoxycarbonyl, acyl, ammonio, alkylammonio, trialkylammonio,benzyl-dialkylammonio, alkoxy, alkylthio, halogenalkyl, optionallysubstituted phenyl or phenoxy radicals, heterocyclic radicals such asthe piperazino or morpholino radical.

Compounds of Formula I bearing substituents which are capable of saltformation with acids, e.g., the amino or dialkylamino group or thetrialkylammonio group, or with bases, e.g., a carboxyl or a phenolichydroxyl group, can also be in the form of their salts and are then ofthe same utility as mentioned hereinbefore.

Preferred compounds falling under Formula I in which Y representssulphur are those of the formula wherein R represents lower alkyl,chloro-lower alkyl, hydroxy-lower alkyl, lower alkanoyloxy-lower alkyl,chlorolower alkanoyloxy-lower alkyl, lower alkyl-sulphonyloxyloweralkyl, lower alkanoyl-lower alkyl, benzoyl-lower alkyl, loweralkanoyl-amino-lower alkyl, amino-lower alkyl, N-alkylated amino-loweralkyl, morpholino-lower alkyl, piperidino-lower alkyl, lower alkanoyl,N-lower alkyl-substituted amino-thiocarbonyl, morpholino-thiocarbonyl,piperidino-thiocarbonyl, pyrrolidino-thiocarbonyl, loweralkoxy-thiocarbonyl, imidazolinyl, chlorodithiolonyl, thenyl,chloro-thenyl, lower alkyl-thiazolyllower alkyl, pyridyl-lower alkyl,carbamoyl-lower alkyl, N-alkylated carbamoyl-lower alkyl,alkoxy-carbonyllower alkyl wherein alkoxy has from 1 to 12 carbon atoms,carboxyl-lower alkyl, lower alkoxy-lower alkoxycarbonyl-lower alkyl,cycloalkyloXycarbonyl-lower alkyl, thienyl, thiadiazolyl,mercapto-thiodiazolyl, aminothiadiazolyl, lower alkylthio-thiadiazolyl,oxazolyl, benzoxazolyl, oxazolinyl, thiazolyl, lower alkyl-thiazolyl,ower alkylthiazolyl-lower alkyl, lower alkoxy-carbonyl-lower alkylthiazolyl, thiazolinyl, benzimidazolyl, pyridyl, N-oxidopyridyl, loweralkoXy-substituted l',3,5'-triazinyl or 2- chloro-4'-loweralkoxy-1,3',5-triazinyl-(6), or monoto tricyclic cycloalkyl of from 5 to10 carbon atoms.

Other compounds falling under Formula X of similar good antimicrobialproperties are those in which R represents acetamido-thiadiazolyl,dialkylformylimino-thiadiazolyl, oxadiazolyl or lower alkyl-oxadiazolyl.

Preferred compounds falling under Formula I in which Y represents -S0-or --SO --are those of the formula wherein Y represents SO- or SO Rrepresents chlorine or lower alkyl, and

R represents lower alkyl, chloro-lower alkyl, hydroXylower alkyl, loweralkanoyloxy-lower alkyl, chlorolower alkanoyloxy-lower alkyl, loweralkyl-sufonyloxy-lower alkyl, lower alkanoyl-lower alkyl, benzoylloweralkyl, lower alkanoyl-amino-lower alkyl, N-alkylated amino-lower alkyl,morpholino-lower alkyl, phenyl-lower alkyl, lower alkyl-phenyl-loweralkyl, chloro-phenyl-lower alkyl, bromo-phenyl-lower alkyl,nitro-phenyl-lower alkyl, naphthyl-lower alkyl, phenyl, loweralkyl-phenyl, chloro-phenyl, bromophenyl, nitrophenyl, carboxy-phenyl,alkoxycarbonylphenyl, hydroxyphenyl, lower alkanoyl-oxyphenyl,aminophenyl, methoxyphenyl, naphthyl, thenyl, chloro-thenyl, loweralkylthiazolyl-lower alkyl, pyridyl-lower alkyl, carbamoyl-lower alkyl,N-alkylated carbamoyl-lower alkyl, alkoXycarbonyl-lower alkyl whereinalkoxy has from 1 to 12 carbon atoms, carboxyl-lower alkyl, loweralkoxy-lower alkoXy-carbonyl-lower alkyl, cycloalkyloxycarbonyl-loweralkyl, thienyl, thiadiazolyl, aminothiadiazolyl, benzoxazolyl, loweralkyl-thiazolyl, lower alkyl-thiazolyl-lower alkyl, loweralkoxy-carbonyllower alkyl-thiazolyl, phenyl thiazolyl, benzothiazolyl,benzimidazolyl, pyridyl, benzimidazolyl-lower alkyl,

pyridyl-lower alkyl, lower alkoxy-substituted 1,3',5'- triazinyl or2-chloro-4'-lower alkoxy-l,3,5-triazinyl- (6), or monoto tricycliccycloalkyl of from to 10 carbon atoms.

Most preferred compounds falling under Formula X1 in which R, is halogenor lower alkyl, and Y is SO are those of the formula (XII) wherein Rrepresents halogen or lower alkyl, and

R represents lower alkyl, phenyl, lower alkyl-substituted phenyl,thienyl, lower alkyl-substituted thienyl, pyridyl or lowerlakyl-substituted pyridyl.

Most preferred compounds falling under Formula XI in which R, is aphenyl or lower alkyl-phenyl radical are those of the formula R (XIII)wherein Y represents SO-- or -SO R represents phenyl or loweralkyl-phenyl, and R represents lower alkyl.

Preferred salts falling under Formula I are those of the formula (XIV)wherein Y represents -S-, -SO or -SO R represents N-alkylatedammonio-lower alkyl or N- benzyl ammonio-lower alkyl, and

A- represents the equivalent of a monovalent anion.

The invention is further illustrated by the following nonlimitativeexamples. Where not expressly stated otherwise, parts and percentagesare given by Weight. The temperatures are in degrees centigrade.

EXAMPLE 1 EXAMPLE 2 41.5 parts of Z-phenyl-ethyl mercaptan are addeddropwise to a suspension of 33.7 parts of magnesium carbonate and 56.1parts of 4,5-dichloro-1,2-dithiol-3-one in 250 parts by volume ofethanol, the addition being made within 75 minutes while stirring at aninner temperature of 510. The whole is then stirred for 12 hours at roomtemperature after which it is filtered. The filter residue is extractedwith benzene. The filtrate is evaporated under reduced pressure and theevaporation residue is also extracted with benzene. The combined benzeneextracts are 8 concentrated to a small volume. On cooling, 80.9 parts(93.4% of the theoretical) of pure (4-chloro-l,2-dithiol-3-on-5-yl)-(2'-phenylethyl)-sulphide crystallise out, M.P. 85.5-96.5.

EXAMPLE 3 A solution of 18.71 parts of 4,5-dichloro-1,2-dithiol-3- onein 70 parts by volume of dimethyl formamide is cooled to -70". 22.23parts of Z-mercapto pyridine are added all at once and the mixture isstirred without cooling until it has attained room temperature. Thereaction product precipitates during this time in long fine needleswhich are filtered off and washed with water. This first crystallisateweighs 21 parts. On diluting the mother liquor with water, another 4.5parts of (4-chloro-l,2-dithiol-3-on-5-yl)-(2-pyridyl)-sulphide areobtained.

The total yield is 25.5 parts (97% of the theoretical). The meltingpoint is 148-1495 EXAMPLE 4 42.1 parts of thioglycolic acid ethyl esterare quickly added to a suspension of 98.7 parts of barium carbonate and56.1 parts of 4,5-dichloro-1,2-dithio1-3-one in 300 parts by volume of96% ethanol, the addition being made while stirring at an innertemperature of l0 An exothermic reaction immediately takes place. Thetemperature is prevented from rising above 20 by cooling. On completionof the main reaction, the whole is stirred for 3 hours at roomtemperature and then filtered. The filter residue is washed twice with250 parts by volume of methylene chloride each time and then thrownaway. The combined filtrates are concentrated under reduced pressure toa small volume. On cooling, 61.3 parts (75.5% of the theoretical) ofpure (4-chloro-1,2-dithiol-3-on-5- yl) (ethoxy-carbonylmethyl) sulphidecrystallise out; M.P. 5657.

EXAMPLE 5 27.5 parts by volume of about aqueous thioglycolic acid areadded all at once to a suspension of 37.4 parts of4,5-dichloro-1,2-dithiol-3-one in 150 parts by volume of methanol, theaddition being made while stirring at 40 to 50. The mixture is thenstirred for another 12 hours, the temperature being gradually brought toroom temperature. It is then filtered. The filter residue is washed witha little methanol, dried and extracted with 250 parts by volume of hotchloroform. The chloroform extract is evaporated and the evaporationresidue is recrystallised from methanol. 27.2 parts (53.0% of thetheoretical) of pure (4-chloro-1,2-dithiol-3-on-5-yl)(methoxy-carbonylmethyl)-sulphide are obtained; M.P. 99-l00.5. 15.3parts (31.5% of the theoretical) of (4-chloro-l,2-dithiol-3-on-5-yl)-(carboxymethyl) sulphide (M.P. 203-205were insoluble in chloroform.

If the same reaction is performed in water, then (4-chloro-1,2-dithiol-3-on-5-yl) (carboxymethyl) -sulphide is obtained assole reaction product. It can be converted into the methyl ester in theusual way, e.g., by reaction with methanol in the presence of mineralacid.

EXAMPLE 6 A solution of 22.65 parts of Z-mercapto benzoxazole and 8.10parts of sodium methylate in parts by volume of ethanol is poured within3 minutes into a solution of 30 parts of 4,5-dichloro-1,2-dithiol-3-onein a mixture of 60 parts by volume of acetone and 60 parts by volume ofethylene glycol monomethyl ether, the addition being made while stirringat an inner temperature of -20. The solution is then seeded whereuponthe product quickly crystallises out. After one hour standing at roomtemperature, it is filtered off and washed first with a little acetoneand then with a large quantity of water. The crude product isrecrystallised from ethylene glycol monomethyl ether. The yield of(4-chloro-1,2-dithi0l-3-on-5- yl)-benzoxazolyl-(2)-sulphide, M.P. 138,is 37.0 parts (82% of the theoretical).

9 EXAMPLE 7 A solution of 51.1 parts of ethylene thiourea and 93.5 partsof 4,5-dichloro-1,2-dithiol-3-one in 600 parts by volume of ethyleneglycol monomethyl ether is heated for 20 hours at 60-70". After cooling,it is filtered. The filter residue is dissolved in a warm mixture of 100parts by volume of Water and 400 parts by volume of chloroform. Theaqueous phase is extracted with 200 parts by volume of fresh chloroform,treated with charcoal and evaporated. The evaporation residue is treatedwith 100 parts by volume of warm ethylene glycol monomethyl ether. 93parts (64% of the theoretical) of(4-chloro-1,2-dithiol-3-on-5-yl)-(imidazolin-2-yl) sulphidehydrochloride remain undissolved. The product decomposes at 160-175depending on the rapidity with which it is heated. The chloroformextracts are evaporated and the residue is recrystallised several timesfrom ethylene glycol monomethyl ether. 6 parts (7% of the theoretical)of bis-(4-chloro-1,2-dithio1-3-on-5-yl)-sulphide are obtained; M.P. 112.

EXAMPLE 8 A solution of 8.5 parts of piperidine, 7.6 parts of carbondisulphide and 5.4 parts of sodium methylate in 100 parts by volume ofethanol are added dropwise to a suspension of 18.7 parts of4,5-dichloro-1,2-dithiol-3-one in 50 parts by volume of acetone and 80parts by volume of ethanol, the addition being made within 2 hours whilestirring at an inner temperature of -30 to -40. On completion of thedropwise addition, the wholeis stirred for another 2 hours withoutcooling, whereupon it is then cooled to -40 and filtered. The filterresidue is washed with water and recrystallised from ethylene glycolmonomethyl ether to which about of water are added. 20.0 parts (64% ofthe theoretical) of pure (4-chloro-1,2-dithiol-3-on-5-yl)-(piperidino-thiocarbonyl) sulphide are obtained;M.P. 120.

EXAMPLE 9 100 parts by volume of ethanol and 30.5 parts of carbondisulphide are added to a solution of 16.8 parts of potassium hydroxidein parts by volume of water. The mixture obtained is added within 10minutes to a suspension of 56.1 parts of 4,5-dichloro-1,2-dithiol-3-onein 80 parts by volume of ethanol the addition being made within 10minutes while stirring and cooling with ice. The whole is stirred foranother 10 minutes at room temperature, filtered and the filter residueis dissolved in as little as possible hot benzene. This solution istreated with charcoal and allowed to crystallise. 40.0 parts (49% of thetheoretical) of (ethoxy-thiocarbonyD-(4-chloro-l,2-dithiol-3-on-5-yl)-sulphide are obtained; M.P. 96-l01. A sample againrecrystallised from benzene melts at 99- 101. The benzene mother liquorsare evaporated and the residue is recrystallised from ethylene glycolmonomethyl ester. 12.4 parts of the theoretical) ofbis-(4-chloro-1,2-dithiol-3-on-5-yl)-sulphide are obtained; M.P. 112.

EXAMPLE 10 A mixture of 2.7 parts of .(ethoxy-thiocarbonyl)-(4-chloro-1,2-dithiol-3-on-5-yl)-sulphide, 5.4 parts of ethyl iodide and 10parts by volume of ethanol is heated for 2 hours at 80. A clear solutionis formed. On cooling, 1.8 parts (85% of the theoretical) of4-chloro-5-ethylthio- 1,2-dithiol-3-one crystallise out; M.P. 102-104.

EXAMPLE 11 A mixture of 3.1 parts of (piperidino-thiocarbonyl)-(4-chloro-l,2-dithiol-3-on-5-yl)-sulphide, 3.4 parts of benzyl bromide and10 pants by volume of ethylene glycol monomethyl ether is heated for 3hours at 80. The solution formed is then poured into water. The productprecipitates in crystalline torm and is liberated from benzyl bromide byboiling out with a little ethanoL. 2.3 parts 10 (84% of the theoretical)of 4-chloro-5-benzylthio-1,2- dithio1-3-one are obtained; M.P. 98.

EXAMPLE 12 28.9 parts of(4-chloro-1,2-dithiol-3-on-5-yl)-(imidazolin-2-yl)-sulphidehydrochloride, 19.9 parts of w-bromoacetophenone, 30 parts by volume ofethanol and 40 parts by volume of water are stirred for 4 hours at Thehot mixture is filtered. The filter residue is washed with methanol andwater and then recrystallised from ethylene glycol monomethyl ether.19.9 parts (65% of the theoretical) of (4-chloro-1,2-dithiol-3-on-5-yl)(benzoylmethyl)sulphide are obtained in this Way; M.P'. 142.

The sulphides of 1,2-dithiol3-ones given in the following Table I areproduced in the manner described in Examples 1 to 12 by reacting a4-chloroor 4-aryl-5-chloro- 1,2-dithiol3-one with a thiol or a salt of athiol.

TABLE I Melting point No. Compound in C.

1 (4-chloro-1,2-dithi0l-3'on-5-yl)-(methyl-sulphlde. 118 2.(4-ehloro-1,2'dithiol-3-0n'5-yl)-(ethyl)-sulphide... 104 3-(4-chlo1'o-l,2rdithiol-3-on-5-yl)-(n-propyl)-sul hid 60 4.4-chloro-l,2dithlol-3-on-5-y1)-(acotylmethyl -sulpl1lde 99 5l-chlotrpl,2-dithiol-3-0n-5y1)-(benzoylmethyl)- 140 su p 11 e. 6.(4-cliloliiol2dithiol-ll on-fi-yl)-(carboxymethyl)- 209 S11 p 1 e. 7(4-chlo1o-l ,2-dlthiol-3-on-5-yD-(diethylamlnoethyl) 33 sulphide. 8-....(4-chloro-1,2-dithlol-3-on-5-yl)-(dlethylamiuoethyl)- 153 sulphide,hydrochloride. 9 (4-chloro-1,2dithiol-3-on-5-yl)-(diethylamlnoethyl)-147 sulphide, fluoroborate. 1D- (4-chloro-1,2dithiol-3on-5-yl)-(ls0propoxyoarbonyl- 7s methyD-sulphide. 11 (4-chloro-1,2-dithi 0l-3-on 5 -y1)-(flmethoxyethoxycar- 49 bonylqnethyD-sulphide. 12 (4-c hloro-l,2dithiol-3-on-5-yl)-(n-dodecyl0xycarb onyl- 61 methyD-sulphide. 13(4-chloro1,2-dithiol-3-on-5-yl) -(carbamoy1methyl) 174 Sn hi e. 14-(4chloro-1,2-dithiol-3-on-5-yl)-(dimethy1carbamoy1- 161methyl)-su1phide. I 16(4cl}lorod1,2-dithioL3-on-5-yl)-(2,4-d1methylphenyl)- 112 su phi e. 16.(4echloro-l,2-dithiol-3-on-5-yl)-(phenyl) sulphide.-. 154 17. (44lilofipl,2-(lithiol-3-on-5-yD-(4-methylphenyl)- 117 su p l. e. 18.(4-chloro1,2-dithiol-3-on-5-yl)-(2,5-dlchlorophenyl)- 120 su phi e. 19(4-chlor0-1,2-dithiol3bn-5-yl)-(pentach10rophenyl)- 151 su hi e. 20.(t-chime?,2-dithiol-3-on-5-yl) -(4-nitr-ophenyl)- 149 Sn phi e. 21(4-chl0gp1,2-dithlol-3-on-5-yl)-(2'-isopropylphenyl)- 113 sn 1 e. 22.(4-ehloro-1,2-dlthlol-3-on-5-yl)-(benzyl)-sulphide 98 23(4-chlorp-1,2-dithiol-3-on-5yl) -(2chlorobcnzyl) 96 yl)-su1phide.

See footnote at end of table.

TABLE I--Con tinued Melting point No. Compound in C.

45- 4chloro- 1,2-dlthiol-3-on-5-yl)-(4-earboxy-methyl- 150thiazol-2-yl)-sulphide. 46-(4-chl0ro-1,2dith1ol-3-on-5-yl)-[4-(ethoxycarbonyD- 69methyl-thlazol-2-yl]-sulph ide. 47- (4chloro-1,2-dlthiol-3-on-5-yD-(4'-phenylthiazo1- 122 2-yl)-sulphide. 48-(4-olilofifli1,2-d1thiol-3-on-5-yD-(benzthiazol-2-yl)- 162 su p e. 49(4-ohloro-1,2-dithlol-3-on 5-yl)-(2-thlono-3H-1 ,3 ,4- 172thladiazolln-5-yl)sulphide. 60.(4-eh10ro-1,2-dlth1o1-3-on-5-yl)-(2-lmlno-3H-1,3,4- 100-200thiadiazolin-B'-yl) sulphide. 61- (4-chloro-1,2-dithiol-3-on-5-yl)-(2-thiono-3-phenyl- 132 1,3',4-thiadiazolin-5-yl)-sulphide. 52.(4-chl0r0-1,2-dithiol-3-on-5-yl) -[adamant-(1)-yl]- 70-71 sulphide. 53-(4-ohloro-1 ,2-dlthlol-3-ou-5-yl)-(cyolohexyloxy- 57-58carbonyl-methyl)-sulphide. 54. (4-chloro-1 ,2-dithiol-3-on 5-yl)-(2-metl1y1-1,3,4- 149. 5-150 oxadiazl-5-yl) -sulphlde. 55-4-chloro-5-aeetylthio-1,2-dithlol-3-one 118 56-(4-chloro-1,2-dithiol-3-on-5-yl)-[(morpholln0)- 192thiocarbonyH-sulphide. 57-(4-ehloro-1,2-dithiol-3-on-5-yl)-[(dimethylamino) 1 61 thioearbonylsulphide. 58- (4-ehloro-1,2-dl ..hlo1-3-on-5-yl) -[(diethylanuno)- 114thioearbonyl sulphide. 59-(4-chloro-l,2dithiol-3-on-5-yl)-(is0propyl)-sulphlde 54-55Decomposition.

EXAMPLE 13 A solution of 71.0 parts of sodium thiosulphate in 50 partsby volume of water is added dropwise within 6 minutes to a solution of93.5 parts of 4,5-dichloro-1,2- dithiol-3-one in 350 parts by volume ofethylene glycol monomethyl ether. During the addition the mixture isstirred vigorously and kept at 0-5 by intensive cooling. The reactionproduct crystallises out. On completion of the dropwise addition, thewhole is stirred for another 15 minutes at 30, then cooled to 15 and thecrystallisate is filtered off. It is boiled with 200 parts by volume ofethylene glycol monomethyl ether, cooled to and again filtered.Non-reacted 4,5-dichloro-1,2-dithiol-3-one is removed in this way. Thefilter residue is bis-(4-chloro- 1,2-dithiol-3-on-5-yl)-sulphide whichmelts at 112. The yield is 53.5 parts (63.8% of the theoretical).

EXAMPLE 14 A mixture of 37.4 parts of 4,5-dichloro-1,2-dithiol-3- one,18.8 parts of thioacetamide, 25.2 parts of magnesium carbonate and 150parts by volume of methanol is stirred for 30 hours at 20 and thentreated with a mixture of 300 parts by volume of methylene chloride and50 parts by volume of water. After filtration, the methylene chloridelayer is removed, extracted with 50 parts by volume of water, dried,treated with charcoal and kieselguhr and concentrated. The evaporationresidue is dissolved in 150 parts by volume of boiling trichloroethyleneand 80 parts by volume of cyclohexane are added to the solution. 8.7parts (26% of the theoretical) of pure bis-(4-chloro-1,2-dithiol-3-on-5-yl) -sulphide crystallise out; M.P. 112.

EXAMPLE 15 19 parts by volume of an about 40% solution of peracetic acidin aqueous acetic acid are added to a suspension of 25.7 parts ofv(4-chloro-1,2-dithiol-3-on-5-y1)- ([methoxycarbonyl]-methyl)-sulphidein 140 parts by volume of acetic acid, the addition being made within 15minutes while stirring at an inner temperature of 4548. It is then leftto stand for an hour whereupon the reaction product partly crystallisesout. The greater part of the solvent is then distilled off under reducedpressure and the product is filtered off. It is washed with a littlemethanol and recrystallised from benzene. 17.9 parts (66% of thetheoretical) of (4-chloro-1,2-dithiol-3-on-5- yl)-[(methoxycarbonyl)methyl] sulphoxide are obtained; M.P. 123.

12 EmMPLE 16 2.1 parts of m-chloro-perbenzoic acid are added to asolution of 2.1 parts of (4-chloro-1,2-dithiol-3-on-5-yl)-(ethyl)-sulphide in 30 parts by volume of benzene, the additionbeing made within 15 minutes while stirring. During the addition, thetemperature is kept at 2225 by cooling. The whole is then stirred foranother 30 minutes at 22 and afterwards filtered. The filtrate is shakenwith 20 parts by volume of sodium bicarbonate solution. The organicphase is then separated, dried and evaporated. The evaporation residueis recrystallised twice from methanol. 1.7 parts (75% of thetheoretical) of (4-chloro-1,2- dithiol-3-on-5-yl)-(ethyl)-sulphoxide,M.P. 94, are obtained.

EXAMPLE 17 5 parts by volume of 4.5% peracetic acid in glacial aceticacid are added dropwise to the solution of 7.1 parts of (4 chloro1,2-dithiol-3-on-5-yl)-(2-chlorobenZyl)-sulphide in 30 parts by volumeof methylene chloride, the addition being made within 1 hour at an innertemperature of 5-10 while stirring. The whole is then stirred for 2hours while cooling with ice. The methylene chloride is distilled offand the oil which remains is dissolved in 15 parts by volume ofmethanol, whereupon 6.8 parts (91% 0f the theoretical) of pure(4-chloro1,2- dithiol-3-on-5-yl)-(2 chlorobenzyl) sulphodixe, M.P.l35-136, crystallise out.

The sulphoxides of 1,2-dithiol-3-ones given in the following Table IIare produced by oxidation of corresponding sulphides according to theprocesses described in Examples 15 to 17.

TAB LE II Melting point No. Uompound in C.

1 (4-chloro-l,2-dithiol-3-on-5yl)-(ruethyl)-s ulph0xide...- 178 2.(4-chlo1'o-1,2-dithiol-30n-5-yl)-(n-propyl)-Sulphoxide- 118 3-(4-chloro-1,2-dithiol-3-on-5-yl)-(ethoxycarbouyl- 96 methyl)-sulphoxide. 4- (4-ehloro-1,2-dithiol-8-on-5-yl)-(isopropoxy-carbonyl-84 methyl) -sulphoxide. (4-chloro-l ,Z dith iol-3-on5-yl)-(n-dodeeyloxycarbonyl- 61 me th yl)'sulpl1 oxide. 6- (4chloro1,2-dithiol-3-on-5-yl)-(2-cl1loroothyl) 16 1 sulphoxide. 7-(4-chloro-1,2-dlthiol-3-on-5-y)-(2'-aeetoxyethyl)- 124 sulphoxide. 8.(4ehloro1,2-dithiol-3-on-5-yl) -(carbamoylmeth yl)- 175 sulphoxida. 9-(4-ehl0ro-1,2-dithiol-3-ou-5-yl)-([dimethylcarbamoyl) l 173 mathyl]-sulphoxide. 10. (4-chloro-1,2-dithlol-3-on-5-yl)-(benzylmethyl)- 156sulphoxide. 11 (l-chloro-1,2-dithiol-3-on-5-yl)-(phenyl) sulphoxlde..124 12. (4-ohloro-1,2-dith1ol-3-on-5-yl)-(4-methylphenyl)- 177sulphoxide. 3. (4-ehloro-1,2-dithiol-3-on-5-yl)-(2-isopropyl-phenyl)- Sulphoxide. 14. (4-chloro-1 ,2-dithiol-3-ou-5-yl)-(4-nitropl1enyl) l 222sulphoxide. 15. (4-chloro-1,2-dithlol-3-on-5-yl)-(2,4-dimethylphenyl)-sulphoxide. 16- (4-chlor0-1,2-dithiol-3-on 5'yl) -(benzyl) -sulphoxide.17- (4-chloro-1,2-dithiol-3-on-5-yl)-(4-nitrobenzyl)- 179 sulphoxide. 18(4-chloro-1,2-dithio1-3-on-5-yl) -(2,4-dimethylbenzyl) 145 sulphoxide.19- (4-ch1oro-1,2-dithio1-3-on-5-yl) -[(1'-naphthyl) 159 methyl]-sulphoxide. 20- (4-chloro-1,2-dithiol-3-on-5-yl)-(4-bromobenzyl)- 177sulphoxide. 21 (4-eh1oro-1,2-dithiol-3-on-5-yl) -(4-methylb enzyl) 170sulphoxide. 22- (4-ehlo1'0-1,2-dithiol-3-on-5-yl) -(3-chlorob enzyl)sulphoxide. 23 (4421110ro-1,2-dithiol-3-on-5-yl)-[(2'-phenyl)-ethyl]-102 sulphoxide. 24- (4-ehloro-1,2-dithiol-3-on-5-yl)-(2-pyridyl)-sulphoxide.- l 159 25 (4-chloro-1,2-dithiol-3 on-5yl)-(4'-phenylthiazo1-2-yl) 1 208 sulphoxide. 26(4-eh1oro-1,2-dithiol30n5-yl)-(thenyl) -sulphoxide- 125 27- l-chloro-l,2-dithiol-3-on-5-y1) -[(2'-methylthiazol-4-yl) 176 methyH-sulphoxide.28 (4-chlo r0-1.2-dithiol-3-on-5-yl) -[2-(triehlor-acetoxy) 112 ethyl]-sulphoxide. 29- (4-ehloro-1,2-dithiol-3-on-5-yl) -[2-(methanesulphonyl-146 oxy) -ethyl]-sulph0xide. 30. (4-chloro-l.2-dithiol3-0n-5-y])-(isopropyl) -sulphoxide 196-107 31 (4-chlorol,2-dithiol-3-on-5-yl){adamant-(1) -yl]- 143 sulphoxide. 32(4-phenyl-1,2-dlthiol-3-on-5-yl) -(rnethyl) -sulphoxide 33(4-phenyl-1,2-dithiol-3-on-5-yl) -(ethyl) -sulphoxide l Decomposition.

13 EXAMPLE 18 3.2 parts of methyl iodide and 2.0 parts of sodiumbicarbonate are added at room temperature to the solution of 6.0 partsof (4-chloro-1,2-dithiol-3-on-5-yl)-(2'-thiono-3'H-l',3,4'-thiadiazolin-5'-yl)-sulphide in 20 parts by volume ofdimethylformamide and the mixture is stirred until, after about 15minutes, it has solidified into a thick slurry. 50 parts by volume ofwater are added, it is filtered, the filter residue is Washed first with20 parts by volume of ethanol and then with 100 parts by volume of waterand is recrystallised from 15 parts by volume of dimethyl formamide. 5.3parts (84% of the theoretical) of pure(4-chloro-1,2-dithiol-3-on-5-yl)-(2 methylthio 1',3,4'-thiadiazol--yl)-sulphide are obtained which melts at 124-125 Thecompounds mentioned in the following Table III are produced by theprocess described in Example 18.

thiadiazol-5-yl)-sulphide.

EXAMPLE 19 60 parts by volume of thionyl chloride are poured over 22.9parts of (4 chloro 1,2 dithiol 3 on 5 yl)- (2'-hydroxyethyl)-sulphide.First, with strong gas development, a clear solution is formed fromwhich a precipitate begins to separate out. After completion of the gasdevelopment, the whole is heated for 1 hour at 95- 100. It is thenfilered and the filtrate is evaporated. The evaporation residuecrystallises on stirring with ice water; the crude yield is 22.5 parts(91% of the theoretical). Recrystallisation from ethanol yields 19.0parts (77% of the theoretical) of pure (4-chloro-1,2-dithiol-3-on-5-yl)(2'-chloroethyl)-sulphide, M.P. 6464.5.

EXAMPLE 20- A mixture of 22.9 parts of (4-chloro-l,2-dithiol-3-on-5-yl)-(2'-hydroxyethyl)-sulphide, 37 parts of trichloracetic acidanhydride, 100 parts by volume of dichloromethane and 0.2 part by volumeof 96% sulphuric acid is refluxed for 1 hour. All volatile componentsare then distilled off at 80/ 15 torr. The oily residue crystallisesafter two days Recrystallisation from ether yields 26.2 parts (81% ofthe theoretical) of pure (4-chloro-1,2-dithiol-3-on-5-yl)-[(2-trichloracetoxy)-ethyl]-sulphide, M.P. 63.

EXAMPLE 21 A suspension of 9 parts of (4-chloro-1,2-dithiol-3-on-5- yl)(2' imino-3'H-l',3,4-thiadiazolin-5'-yl)-sulphide in 100 m1. ofacetanhydride is refluxed for 1 hour. After cooling, the reactionproduct is filtered off and recrystallised from ethylene glycolmonomethyl ether, 5 parts (50% of the theoretical) of (4-ch1oro1,2-dithiol-3-on- 5 yl) (2-acetylamino-1',3',4-thiadiazol5'-yl)-sulphideare obtained. It decomposes at 225-227".

EXAMPLE 22 6 parts of phosphorus oxychloride are added dropwise within10 minutes to 20 parts by volume of dimethyl formamide, the additionbeing made while cooling with ice. A solution of 4.4 parts of(4-chloro-1,2-dithiol-3-on- 5 yl)(2'-imino-3H-1,3',4'-thiadiazolin-5'-yl)-sulphide in 20 parts ofdimethyl form-amide is added to the solution obtained. The reactionproduct which crystallises out is filtered off and washed, first with aslight amount of dimethyl formamide, then with sodium bicarbonatesolution and finally with water. The crude product is recrystallisedfrom ethylene glycol monomethyl ether. 3.0 parts (54% of thetheoretical) of (4-chloro-l,2-dithiol- 3 on 5yl)-[2'-(dimethylaminoformylimino)-1',3',4'- thiadiazol-5'-yl]-sulphide,M.P. 170-171 are obtained.

EXAMPLE 23 11.6 parts of triethylamine are added dropwise to a mixtureof 22.9 parts of (4-chloro-l,2-dithiol-3-on-5-yl)-(2'-hydroxyethyl)-sulphide, 13.1 parts of methane sulphochloride and 200parts by volume of dichloromethane,

the addition being made within about 5 minutes at 20 while stirring.Stirring is continued for another 10 minutes without cooling and thenthe precipitated triethylamine hydrochloride is filtered ofi. Thefiltrate is washed twice with water and dried with magnesium sulphate.After distilling off the dichloromethane, an oil remains. This isdissolved in 50 parts by volume of ethylene glycol monomethyl ether; thesolution is seeded and cooled to 0. The product slowly crystallises out.It is filtered off, washed with methanol and dried in the air. 25.0parts (82% of the theoretical) of 4-chloro-1,2-dithiol-3-on-5-yl)-[2'-(methane sulphonyloxy)-ethyl]-sulphide are obtained, M.P. 86". A samplerecrystallised from isopropanol melts at 89.

EXAMPLE 24 A mixture of 28.4 parts of (4-chloro-1,2-dithiol-3-on-5-yl)-(2-diethylaminoethyl)-sulphide, 15.0 parts of allyl bromide and 15parts by volume of acetone is refluxed for 1 hour. After cooling, thecrystalline reaction product is filtered 01f, washed with a littleacetone and dried. 37.3 parts (92% of the theoretical) ofdiethyl-allyl-2-(4'- chloro 1',2dithiol-3'-on-5'-yl-thio)-ethyl-ammoniumbromide are thus obtained; M.P.183 (with decomposition).

In addition, the following compounds are produced by the processdescribed:

EXAMPLE 25 48.2 parts of dimethyl sulphate are added dropwise to asuspension of parts of the dimethyl ammonium salt of4-phenyl-5-mercapto-1,2-dithiol-3-thione in 500 parts of methanol, theaddition being made within 35 minutes While stirring at an innertemperature of 10-15". (The above mercapto compound is produced byreacting Otmethylstyrene with sulphur in the presence of dimethylformamide, cf. British Pat. No. 1,049,637.) The whole is then stirredfor 2 hours at 15-20 inner temperature, then cooled to 30 and filtered.The filter residue is recrystallised from ethylene glycol monomethylether. 74.4 parts of 4-phenyl-5-methylthio-l,2-dithiol-3-thione, M.P.-126 are obtained.

The solutions of 20 parts of 4-phenyl-5-methylthio-1,2- dithiol-3-thionein parts of chloroform and of 50 parts of mercury-(ID-acetate in 1000parts of glacial acetic acid are combined. The mixture is left to standfor 3 days at 20-23" after which it is filtered. The filtrate is shakenthree times with 500 parts of water each time, dried over magnesiumsulphate and concentrated. The residue is dissolved in boiling ethyleneglycol monomethyl ether. On cooling, 14 parts (75% of the theoretical)or 4 phenyl 5 methyl-thio-l,2-dithiol-3-one crystallise into needleswhich melt at 103-105".

On using 90 parts of diethyl sulphate instead of the dimethyl sulphatementioned above, and with otherwise the same procedure, 73 parts of4-phenyl-5-ethylthio-l,2- dithiol-3-thione, M.P. 91-92, are obtained,from which 4-phenyl-5-ethylthio-1,2-dithiol-3-one, M.P. 7677, isproduced.

EXAMPLE 26 A solution of 16 parts of potassium permanganate in acetoneis added dropwise to a stirred and ice-cooled suspension of 24 parts of4-phenyl-5-methylthio-1,2-dithiol- 3-thione in 100 parts of acetone andthe whole is then filtered. The filtrate is concentrated, the residue isdissolved in chloroform, again filtered and the filtrate is put into achromatography column filled with silica gel. On eluting with a mixtureof chloroform/hexane, an eluate consisting of pure4-phenyl-5-methylthio-1,2-dithiol-3- one is obtained which melts at103-105 EXAMPLE 27 37.4 parts of 4,5-dichloro-1,2-dithio1-3-one and 40parts of benzene sulphinic acid sodium salt in 300 parts by volume ofmethanol are heated within 30 minutes to 60 while stirring. Part of theproduct crystallises out during this time. To complete the reaction, thereaction mixture is set aside for 2 hours at room temperature, afterwhich 400 parts of Warm Water (70) are added. The reaction product isfiltered off, Washed with water and then dried. The yield of crudeproduct is 56.8 parts=97% of the theoretical. After recrystallisationfrom ethanol, the 4-chloro-S-phenylsulphonyl-1,2-dithiol 3 one obtainedmelts of 121.

EXAMPLE 28 A mixture of 9.3 parts of 4,5-dichloro-1,2-dithiol-3- one, 15parts of 4-toluene sulphinic acid sodium salt and 50 parts by volume ofwater is brought within 2 hours from 50 to 95 while stirring. During theheating, the reaction product crystallises. The reaction mixture is thenfiltered while still warm. The filter residue is washed with water andthen dried. The yield of crude product is 14.1 parts==92% of thetheoretical. Recrystallised from ethanol, the4-chloro-5-(4'-tolylsulphonyl)-1,2-dithiol-3-one obtained melts at 132.

EXAMPLE 29 28 parts of 4,5-dichloro-l,2-dithiol-3-one and 43 parts of S-naphthalene sulphinic acid sodium salt in 50 parts by volume of benzeneand 100 parts of water are heated, while stirring, for 4 hours at 5055and then boiled for 3 hours. The reaction mixture is cooled to and theprecipitate formed is filtered oif. The filter residue is washed withWater and then dried. The yield of crude product is 45 parts=87% of thetheoretical. Recrystallised from isopropanol, the 4chloro-S-(B-naphthylsulphonyl-l,2-dithiol-3-one melts at 132.

EXAMPLE 30 4.65 parts of 4,5-dichloro-l,2-dithiol-3-one and 4 parts ofB-phenylethane sulphinic acid sodium salt in 20 parts by volume ofethanol are boiled for 20 minutes while stirring. Water is then added tothe reaction mixture and the reaction product which precipitates isfiltered off. The filter residue is Washed with water and then dried.The yield is 7.6 parts=95% of the theoretical. The 4-chloro--(fl-phenylethylsulphonyl)-l,2-dithiol 3 one melts at 137.

EXAMPLE 31 3 parts of 4- (4'-tolyl)-5-chloro-1,2-dithiol-3-one and 2.1parts of crude thiophene sulphinic acid sodium salt in 12 parts byvolume of dimethyl sulphoxide are stirred at room temperature for 30minutes and then 50 parts of ice water are added. The reaction productprecipitates.

To purify, it is boiled with 20 parts by volume of ethanol, whereupon itonly partly dissolves, is again cooled and filtered. The yield of crudeproduct is 3.3 parts=76% of the theoretical. On recrystallisation frombenzene/cyclohexane, the 4-(4-tolyl)-5-thienyl-[2"]-sulfonyl 1,2dithiol-3-one melts at 132.

EXAMPLE 32 First, 4 parts of methane sulphinic acid sodium salt and then5.8 parts of 4-phenyl-5-chloro-1,2-dithiol-3-one are added to 30 partsof dimethyl formamide while stirring, the mixture being cooled with icewater. The reaction mixture is then stirred for 60 minutes at roomtemperature whereupon parts of ice water are added. After a short time,the reaction product crystallises out. After filtering off, it is washedwith water and recrystallised from ethanol. Recrystallised from ethanol,the 4- phenyl 5 methylsulphonyl-1,2-dithiol 3 one melts at 153. Theyield of crude substance is 4 parts=58% of the theoretical.

EXAMPLE 33 7.0 parts of 4,5-dichloro-1,2-dithiol-3-one and 10 parts of4-acetamidobenzene sulphinic acid sodium salt are boiled for 45 minuteswhile stirring in 100 parts by volume of methanol. The reaction mixtureis then cooled and the precipitate formed is filtered ofi. The filterresidue is washed, first with 50 parts by volume of hot methanol, thenwith 50 parts by volume of a mixture of methanol and water 1:1 andfinally with water, and dried. Recrystallized from ethylene glycolmonomethyl ether (methyl Cellosolve), the4-chloro-5-(4'-acetamidophenylsulphonyl-1,2-dithiol-3-o ne obtainedmelts at 234-236". In order to saponify the acetamido group, 50 parts byvolume of methyl Cellosolve and 20 parts by volume of concentratedaqueous hydrobromic acid can be added to this substance. The mixture iskept for 2 hours at 70-75 while shaking now and then. A clear solutionis obtained which is evaporated to dryness. Ice water is added to theresidue and it is neutralised with a little sodium bicarbonate. Theproduct which precipitates is filtered off under suction, washed severaltimes with water and dried. The yield of crude product is 7.3 parts=63%of the theoretical (calculated on the 4,5 dichloro-1,2-dithiol-3-oneused). The 4-chloro-5-(4'-amino-phenylsulphonyl) 1,2 dithiol- 3-oneobtained in this way melts at 191-193 after recrystallisation fromethanol/water.

EXAMPLE 34 A mixture of 1.5 parts by volume of 40% aqueous peraceticacid and 15 parts by volume of glacial acetic acid are added dropwisewithin 1 hour to a solution of 1.18 parts of4-chlor0-5-(4'-chlorophenylthio)-l,2-dithiol- 3-one in 80 parts byvolume of glacial acetic acid, the addition being made while stirring atroom temperature. The whole is then heated for 15 hours at 6770. Theglacial acetic acid is then distilled off and the residue isrecrystallised from ethylene glycol monomethyl ether. The melting pointof the product obtained is (not clear). Chromatographic adsorption insilica gel in chloroform yields pure 4chloro5-(4'-chlorophenylsulphonyl)-1,2-dithiol-3-one from it. The pureproduct melts at 192.

EXAMPLE 35 1300 parts by volume of an about 40% solution of peraceticacid in acetic acid are added within 30 hours to a suspension of 638parts of (4-chloro-1,2-dithiol-3- one-5-yl)-ethyl-sulphide in 200 partsby volume ofglacial acetic acid, the addition being made while stirringat an internal temperature of 3035. The whole is'then stirred for afurther 20 hours at room temperature and afterwards cooled at 10. Thecrystalline reaction product is EXAMPLE 36 4-chloro 5(2'-chlorobenzylsulphonyl)-1,2-dithiol-3- one.

EXAMPLE 37 4-chloro 5 (4'-chlorobenzylsulphonyl)-1,2-dithio1-3- one.

EXAMPLE 38 4-chloro 5 (4'-bromobenzylsulphonyl)-1,2-dithiol-3- one.

EXAMPLE 39 4-chloro 5 (4'-methylbenzylsulph0ny1)-1,2-dithiol-3- one.

EXAMPLE 40 4-chloro 5 [naphth (1') y1methylsulphonyl]-1,2-dithiol-3-one.

EXAMPLE 41 4-(4-chlorophenyl) 5 methylsulphonyl-1,2-dithiol-3- one.

EXAMPLE 42 4- (4-tert.butylphenyl) 5 methylsulphonyl-l,Z-dithiol- 3-one.

EXAMPLE 43 4-chloro-S-carboxymethylsulphonyl-1,2-dithiol-3-one.

EXAMPLE 44 4-ehloro 5 (methoxycarbonyl-methylsulphonyl)-1,2-dithiol-3-one.

EXAMPLE 45 4-chloro 5 (2'-methoxy-ethylsulfonyl)-1,2-dithio1-3- one.

EXAMPLE 46 4-chloro 5 (2'-acetamido-ethylsulphonyl)-1,2-dithiol- 3-one.

EXAMPLE 47 4-chloro 5 (2' diethylamino-ethylsulphonyl)-1,2-dithiol-3-one.

EXAMPLE 48 4-chloro 5 (2-p-tolyl-ethylsulphonyl)-1,2-dithiol-3- one.

EXAMPLE 49 4-chloro 5 (2'-p chloropheny1-ethylsulphonyl)-1,2-dithiol-3-one.

EXAMPLE 50 4-chloro 5 (2'-hydroxy-5'-nitrophenylsulphonyl)-1,2-dithiol-3-one.

EXAMPLE 51 4-chlo1'o 5 (2'-cyanophenylsulphonyl)-1,2-dithiol-3- one.

EXAMPLE 52 4-chloro 5 [2'-bromonaphthyl (1) sulfonyl]-1,2-dithiol-3-one.

EXAMPLE 53 4-chloro 5 (3'-methyl 4ethoxycarbonylphenylsulphonyl)-1,2-dithiol-3-one.

EXAMPLE 54 4-chloro 5 (4'-n-nony1phenylsulphony1)-1,2-dithiol- 3-one.

1 8 EXAMPLE 55 4-chloro 5 (4-phenoxyphenylsulphonyl)-1,2-dithiol- 3-one.

EXAMPLE 56 4-chloro-S-biphenylsulphonyl-1,2-dithiol-3-one.

EXAMPLE 57 4-chloro 5 (4 ethylthiophenylsulfonyl)-1,2-dithiol- 3-one.

EXAMPLE 58 4 chloro 5 (4 dimethylaminophenylsulphonyD-1,2-dithiol-S-one.

EXAMPLE 59 4chloro-S-n-hexylsulphonyl-1,2-dithiol-3-one.

Example M.P., No. Name O 196 122 77 126 644-ch1oro-5-n-butylsulfony1-l,2-dithlol-3-one 69 65..4-ch1or0-5-chl0romethylsulionyl-1,2-dithio1-3-one 136 664-chlor0-5-(2-to1ylsu1fony1)-1,2-dithio1-3-one 107 674-ch10ro-5-(2,5-dimethylphenylsulfonyl)-1,2- 129 dithiol-3-one. 684-ehloro5'(2,4 -dlmethylpheny1sultonyl)-1,2- 92 dithlo1-3-one. G94ghloro-5-(4'-cblorophenylsulfonyl)-1,2-dithiol 192 one. 704-chloro-5-(2,6'-diehlorophenylsulfony1)-1,2- 164 dith1ol-3-one. 714-eh10r0-5-(2',4,5trich1orophenylsulfonyl)-1,2- 180 dithiol-3-one. 724-eh1oro-5-(2,4'-dichloro-5-meth'ylphenylsulfonyl)- 1821,2-dith1ol-3-one. 73 4-chloro-5-(3-earboxyphenylsul1onyl)-1,2- 255dithiol-3-one. 74 4-ch1oro-5-(4-methoxyphenylsulionyl)-1,2- 162dithiol-3 one. 75 4-ehloro-5-[5',6,7,8-tetrahydronaphthyl-(Z)- 148sulfinyl]-1,2-dithiol-3-one. 76 4-ch1or0'5*[thlo11y1'(2' )-su1fonyl]1,2-d thiol-Elbne... 134 77 4-phenyl-5-phenylsulfonyl-1,2-dith1o1-3-0ne117 78 4-phenyl-5-(4-tolylsulfony1)-1,2-dithiol-3-0ne 133 794-(4-tolyl)5-methylsulfonyl-1,2-dithio1-3one 188 804-(4'-tolyl)-5-phenylsu1tonyl-1,2-dithiol-3-one 141 814-ghloro-5-(4'-lsopropylphenylsulfonyl)-1,2-dithiol- -one. 824-ehloro-5'(2',4,6-tr1methylpheny1su1fony1)-1,2-

dithio1-3-one. 83 4-t5hloro-5-(4'-ethylpheny1sultony1)-1,2-dithiol- 90one. 84 4-ehl0r0-5-(3', -dimethy1phenylsu1fony1)-1,2- 147 dithiol-S-one.85 4-eh10r0-5(4-Seo. buty1pheny1sulfonyl)-1,Z- 62 dithi one. 864-eh1oro-fi'benzylsulfonyl-l,2-dithiol-3-one 139 874-pheny1-5-ethylsulfonyl-1,2-dith1iol-3on 113 The phytofungicidalactivity of compounds of Formula I was determined by comparative testson beans.

Leaves of bean plants (Phaseolus vulgaris) in the twoleaf stage weresprayed with an aqueous suspension containing 0.1% of active substance.

The suspension was obtained from a 10% wettable powder by dilution withwater. After drying, the leaves were infested with a fresh suspension ofspores of Uromyces appendiculatus, left for one day in a moist room andthen kept in a greenhouse. The test was evaluated after 7 to 10 days,according to the following comparative scale:

10=full activity (no infestation).

9-1 =decreasing activity.

0=inactive, like the control plants. X=1eaves damaged (burned place orzone). XX=up to /a of the leaf surface damaged.

19 XXX=more than /3 of the leaf surface damaged or leaf and plantrespectively destroyed.

Compound: Results 4-chlor0-S-methylsulfonyl-1,2-dithiol-3-one 104-chloro-S-ethylsulfonyl-1,2-dithi0l-3-one 94-chloro-S-n-butylsulfonyl-1,2-dithiol-3-one 84-chloro-5-chloromethylsulfonyl 1,2 dithiol 3- one 104-chloro-S-phenylsulfonyl-1,2-dithiol-3-one 1O 4-chloro 5(2',4'-dimethylphenylsulfonyl)-1,2-

dithiol-B-one 9 4-chloro-5-(2'-phenylethylsulfonyl) 1,2 dithiol- 3-one 94-chloro-5-thienylsulfonyl-1,2-dithiol-3-one 84-phenyl-5-methylsulfonyl-1,2-dithiol-3-one 84-phenyl-5-(4-tolylsulfonyl)-1,2-dithi0l-3-one 84-(4tolyl)-5-methylsulfonyl-1,2-dithiol-3-one 84-chloro-1,2-dithiol-3-one 4-phenyl-5-chloro (German Patent Application1,126,668) XX 4-p-tolyl-5-chloro (German Patent Application 1,126,668)XXX 4,5 dichloro (German Patent Application The action on bacteria andfungi was determined with cotton treated with compounds according to theinvention of Formula I, by:

(I) Bacteriostatic and fungistatic inhibition test (11) Earth burialtest (III) Mildew spot test The active substance is dissolved in methylCellosolve in such a way that there are 25 g. of active substance perlitre solvent. Boiled cotton fabric (about 85 g./sq. m.) is dipped intothis solution and squeezed out between rollers to 40% moisture content.The content of active substance on the fabric is then 1%. The strips offabric are hung up for 5 minutes in a stream of steam and then dried.The strips are then washed for 2 x15 minutes with 5 g. of soap perlitre, the washing being performed at 40 C., then rinsed twice for 3minutes each time and dried. The following tests serve to evaluate theeifectiveness of this treatment:

(I). Bacteriostatic inhibition test The action on bacteria wasascertained by means of the following bacteriostatic test on thefollowing strains of bacteria: Staphylococcus aureus SG 511, Escherichiacoli NCTC 8196, Bacillus pumilus.

The Agar incorporation test according to Leonard and Blackford was usedas test method. Nutrient agar plates containing 100, 30, and 3 ppm. ofactive substance (p.p.m. means parts of active substance per 10 parts ofdiluent) are inoculated with solutions of the a ove tr i and incubated2X24 hou s a 37- T marginal concentrations inhibiting the growth ofindividual strains are given in the following Table VI:

TABLE VI Staph. E. coli aureus N OTC Bac.

N0. Compound SG 611 8196 pumilus 1 (4-chloro-1,2-dithiol-3-on-5-yl) 1010 10 (methyl) -sulphoxide.

2. (4-chloro1,2-dlthiol-3-on-5-yl)- 10 10 10 (ethyl)-sulphoxide.

3- (4-chloro-1,2-dithiol-3on-5-yl)- 1 30 10 (n-propyl) -su1phoxide.

4- (4-chloro-1,2-dithi0l-3-on-5-yl) 10 30 10 (2-chlorethyl) sulphide.

5- (4-chloro-1,2-dlthiol-3-on-5-y1) 1 30 3 (benzyD-sulphoxide.

6. (4-chloro-1,2-dlthiol-3-on-5-yl) 10 10 10 [(methoxycarbonyl)-methyl]- sul phoxide 8. (4-chloro-1,2-dithiol-3on-5-y1)- 3 10 3(thiazol-2-yl) -snlphide.

9- (4-chloro-1,2-dithioi-3-on-5-y1) -(2- 10 10 pyrldyl) -sulphoxide.

10. (4-chIoro-1,2-dithio1-3-on-5-yl) -(2'- 10 100 10 acetoxyethyl)-sulphox1de.

11. 4 phenyl-5-chloro-1,2-dithiol-3-one 100 100 100 (compound known fromGerman publication open to public inspection No; 1,126,668).

Earth burial test Circular samples of 40 mm. diameter are cut from thesample materials treated by the application method described above andthese are buried in compost earth consisting of 50% by weight of cowdung, 30% by weight of compost and 20% by Weight of sand. The earth has30% relative humidity and is kept at 29 C. After 10 days, the sampleswere removed from the earth, cleaned, conditioned at 20 C. and 65%relative humidity and its mechanical strength is tested in the burstingstrength machine (R. Burgess: J. of Applied Bacteriology 17, 230, 1954).The mechanical strength after the earth burial test is compared withthat of the original material, which was determined before it had beentreated as described above, and is expressed in percent of the originalmechanical strength.

TAB LE VI I Mechanical strength at end of the test No. Compound inpercent 1 (4-chloro-1,2-dithiol-3-on-5-y1) -(4-methylthiaz01- 100 2-yl)-sulphide. 2. (4-ch1oro-1,2-dlthiol-3cn-5-yl) -(b enzoxazol-2'-yl) 100sulphide. 3- (4-ch1oro-1,2-dithiol-3-on-5-y1) -(2-thiazolin-2'-yl) 100sulphide 4. (4-chloro-1,2-dithiol-3on-5-yl) -(5-imluo-4H-1,3,4- 100thiadlazolin-2-yl) -sulphide. 5.(Mhloro-l,2-dithiol-3on-5-yl)-[(piper1dino)- 100 thlocarbonylI-sulphide.6 (4-chloro-1,2-dithiol-3-on-5-yl) -2pyridyl) -su1phide. 100 7.4,5-dichloro-1,2-dithi0l-3-on (German specification 0 open to publicinspection No. 1,102,174). 8. 4-pheny1-5-chloro-1.2-dith1o1-3-one(German specifi- 0 cation open to public Inspection No. 1,126.668).

The fungicidal activity of the new compounds of general Formula XI wasfurther determined by the so-called spore germination test on thefollowing types of fungi:

Alternaria tenuis Botrytis cinerea Clasterosporium c. Coniothyrium dipl.Fusarium culmorum I Mucor spec.

Mucor spec. Penicillium spec. Stemphylium cans.

1 ccm. of a 1%, 0.1% ii 0.01% acetone solution of the active substanceis placed on each of 2 glass slides (26 x 76 min), under the sameconditions. The solvent is evaporated off and a uniform coating ofactive substance is obtained on the glass slides. The slides areinoculated with spores of the above fungi and then kept in dishes atroom temperature in an atmosphere which is almost saturated with steam.The germinated spores are counted twice, first after 2-3 days and thesecond time after 4-6 days. The average is formed from the two valuesobtained. The results are summarised in the fol lowing table.

To lend an effective, broad and protracted protection against fungi to,for example, a paint based on dispersion colours, the procedure can beas follows:

3 parts of active substance are dissolved in 5 parts of a 1:1 mixture ofdimethyl forrnamide and ethylene glycol monornethyl ether. 87 parts (or92 parts or 92.7 parts) of a commercial dispersion colour having afoundation of polyvinyl acetate-ethyl acrylate copolymer are stirredinto this solution, 5 parts of water are added and the whole is stirreduntil homogeneity is attained. Two other paints are produced by the samemethod using 1 or 0.3 part of active substance and 89 or 89.7 partsrespectively of dispersing colour. The 3%, 1% or 0.3% finished coloursso obtained are painted on filter paper, e.g., Whatman 3M M., (320 g.per sq. m.) to test the fungistatic activity; the papers are aired for 8days at and a relative humidity of -90%.

Circular samples of 2 cm. diameter are cut from this filter paper andplaced in Petri dishes each containing 20 ccm. of Sabouraud-Maltose agarinoculated with Pullularia pullulans. The following Table IX shows theconcentration with which there was no growth of fungi Compound 4chlorohrnethylsulphonyld,2-dithlol-3one4-ch1oro-5-ethylsulfonyl-l,2-dlthiol-3-onel-chloro-fi-n-propylsullonyl-l,2-dtthio1-3-one--.4-chloro-5-isopropylsulionyl-1,2dithlol-3-one4chloro5-(fi-phenylethylsulfonyl) -1,2-dithi0l-34-chloro-5-phenylsulionyl-i,2-dithi01-3-one 4-0111010-1,ZdiilhlOlfi-OHBsubstituted in fi-position by:

2(trlchloroacetoxy)ethylthio 2'-(N,N-dlethy1amine)-ethylthio(Methoxycarbonyb'methylthio Dlmethylcarbarnoyl-methylthioBenzoylmethylthio Carboxyrnethylthio ThiazolyHZ) -thio(4-ch10ro-1.2-dithiol-3-on'5y1) -thio A -thiazoliny1-(2)-thio.Thenylthio (4J-chloro the nyl) -thlo (Pyrldyl-[2D-methy1thio.(Diethylamino-thiocarbonyl) -thi0 (Ethoxythiocnrbonyl)-thioMethylsulfinyl B C D E F G H NOTES 2 means an at least 90% inhibition ofgermination effected by the residue of 1 ccm. of a 1% solution of activesubstance.

+ means the same inhibition effected by the residue of 1 com. of a 0.1%solution of the active substance. means the same inhibition effected bythe residue of '1 com. of a 0.01% solution of active substance.

inhibition of germination with the concentrations used.

either on the upper or lower side of the sample or on the surface of theagar under the sample.

Minimum effective con- Compound: centration (in percent) 4 chloro nbutylsulfonyl 1,2-dithiol- 3 one 1 4-chloro 5 chloromethylsulfonyl 1,2dithiol 3 one 0.3 4 chloro 5 (2,5-dichlorophenylsulfonyl- 1,2 dithiol 3one 0.3 4 chloro 5 (2 tolylsulfonyl) 1,2-

dithiol 3 one 1 4-chloro 5 (2',5'-)dimethylphenylsulfony1)- 1,2 dithiol3 one 1 4 chloro 5 (2'4 dimethylsulfonyl)-l,2-

dithiol 3 one 1 4 chloro 5 (3 carboxyphenylsulfonyD- 1,2 dithiol 3 one 14 chloro 5 (4 aminophenylsulfonyl)- 1,2 dithiol 3 one 1 4-phenyl 5-methylsulfonyl 1,2 dithiol- 3 one 03 4 (4' tolyl) 5methylsulfonyl-l,2-dithiol 3 one 50.3 4,5-dichloro 1,2 dithiol 3 one(German Patent Application 1,126,668) 3 4 phenyl 5 -chloro 1,2 dithiol 3one (German Patent Application 1,102,174) 3 4-chloro-1,2-dithiol-3-Effective minimum one substituted in 5- concentration position by: (inpercent) Benzoxazolyl (2) thio 0.3 Benzimidazoly l -(2') thio 0t34-rnethylthiazol 2' yl-thio 60.3 Ethylthio 50 .3 Methylthio 0.3Methoxycarbonyl methyl -thio 50.3 4' chloro 1,2' dithiol 3' onyl (5)-thio 0.3 N-oxido-pyridyl (2') thio 0.3 Benzyl-thio 601.3S'amino-1',3',4'-thiadiazolyl-(2')-thio 50.3 5' methylthio 1',3',4thiadiazolyl (2)- thio 60.3 Ethylsulfinyl 1 Methyl-sulfinyl 0.3 2'chloroethyl thio 0=.3

Compounds:

S-[thiazolyl (2) thio] 4 chloro 1,2-

dithiol 3 one 0-L3 5 phenylsulfinyl 4 chloro 1,2 dithiol- 3 one 0.3 5(2' chlorobenzyl sulfinyl) 4 chloro- 1,2 dithiol 3 one 1 5(isopropoxycarbonylmethyl sulfinyl) 4- chloro 1,2 dithiol 3 one 1 5(ethoxycarbonylmethyl sul'finyl) 4- chloro 1,2 dithiol 3 one 03 Thebactericidal and fungicidal action of 1,2-dithiol- 3-ones according tothe invention were further tested by dissolving 25 g. of the activesubstance to be tested in 1 liter of ethylene glycol monomethyl ether.Strips of cotton fabric which had been washed at the boil (about 85g./l. sq. m.) were dipped in this solution and then squeezed out to aliquor content of 40% by weight, calculated on the dry weight of thefabric, so that the concentration of active substance on the fabric was1% by weight. The strips of fabric were dried for 5 minutes in a streamof steam after which they were washed twice for 15 minutes each timewith a soap solution (5 g. soap/liter of water) at 40 C., then rinsedtwice for 3 minutes each time with cold Water and dried. The fol- 24lowing tests were then made with the strips of fabric so treated:

(a) Inhibition test Circular samples of 2 cm. diameter of said fabricwere placed in Petri dishes on agar culture-medium which had beeninoculated in the usual way with (A) S taplzylococcus aureaus SG 511 (B)Escherichia coli NCTC 8196 (C) Aspergillus niger ATCC (D) Candidaalbicans Results In the following table the symbols signify:

+ :growth of bacteria and fungi on and under sample.

- :110 growth.

A Staphylococcus aureus SG 511.

B Escherichia coli NCTC 8196.

D Candida. albicans.

the fabric Compound 4chloro-5-methylsulfony1-1,2'dithiol-3-0ne4-ehloro-fi-n-butylsulfonyl-l,2-dithlol-3-one4-chl0ro-5-(2-tolylsuli0nyl)-1,2-dith1o1-3-one4-ehloro-5-(4-aminophenylsulionyl)-1,2-dithiol-3-one.4chloro-5-(3-carboxyphenylsulfonyl) -1 2dithlol-3-one-4-chloro-5-(2,4-dichlorophenylsulfonyl) -1 ,2-dithiol-3- (b) Macerationtest Circular samples of 4 cm. diameter of the fabric treated asdescribed above were subjected to maceration in compost consisting of50% cow dung, 30% compost and 20% sand (all percent by weight). The soilhad 30% relative humidity and was kept at 28 C. After 10 days, thesamples were disinterred, cleaned and conditioned at 20 to 24 C. and 65%relative humidity. The tensile strength after the maceration, measuredby the resistance to perforation is compared with that of the fabricbefore the treatment above described, the initial tensile strengthhaving been previously determined. It is expressed in percentage of saidinitial tensile strength.

Compound: Residual tensile strength in percent4-chloro-S-methylsulfonyl-1,2-dithiol-3-one llllllllll llllllllllllllllllll llllllllll 4-chloro-S-ethylsulfonyl-l,2-dithiol-3-one 974-chl0ro-5- (4-sec.butylphenylsu-lfonyl) l ,2-dithiol-S-one 1004-chloro-5'-(2',4'-dimethylphenylsulfonyl)-1,2-

dithiol-S-one 100 4-chloro-5-(2,46'-trimethylphenylsulfonyl)1,2-dithol-3-one 100 4-chloro-5-(2',5-dichlorophenylsulfonyl)-1,2-

dithiol-3-one 100 4-chloro-S-benzylsulfonyl-1,2-dithiol-3-one 1004-chloro-5-(fl-phenyl-ethylsulfonyD-1,2-

dithiol-B-one 100 4-chloro-5-(fi-naphthylsulfonyl)-1,2-

dithiol-3-one 100 (4-chloro-l,2-dithiol-3-on-5yl)-(4'-methylthiazol-2'-yl)-sulfide 100 (4-chloro-1,2-dithiol-3-on-5-yl)-(benzoxazol-2-y1)-sulfide 100 (4-chloro-1,2-dithiol-3-on-5-yl)-'-thiazolin-2'-yl)-sulfide 100 (4-chloro-1,2-dithiol-3-on-5-yl)5'-imino- 4H-1'3,4'-thiadiazolin-2'-yl)-sulfide 100(4-chloro-1,2-dithiol-3-on-5-yl)- [(piperidino)-thiocarbonyl]-sulfide100 Mildew spot test Circular samples of 8 cm. diameter of the fabrictreated as described above were placed on sterile Worth agar platesprepared according to Difco Manual, 9th edition, p. 244, by spreading 15ml. of Worth agar in Petri dishes of 10 cm. diameter and leaving them tosolidify.

The samples were placed on the agar which was then inoculated with aspore suspension containing a mixture of the spores of the fungiChaeromium globosum, Aspergillus niger and T richoderma viride.

The Petri dishes were stored for days at 28 C. and then the growth ofmould was determined.

Results In following table the symbols signify: 0=no growth of mildewspots and mould. +=few mildew spots and little mould growth. ,++=mediumdegree of mildew spots and mould growth.

+++==many mildew spots and strong mould growth.

Compound Result 4-chloro-5-methylsulfonyll ,2-dithiol- 3-one4-chloro-5-ethylsulfonyl-1,2-dithiol-3-one4-chloro-5-(2tolylsulfonyl)-1,2-dithiol- 3-one4-ehloro-5-(4'-tolylsulfonyl)-1,2'-dithiol- 3-one4-chloro-5-(2',4'-dimethylsulfonyl)-1,2-

dithiol-S-one 4-chloro-5-(4'-ethylphenylsulfonyl)-1,2-

dithiol-3-one 4-chloro-5-(4-sec.butylphenylsulfonyl)-1,2-

dithiol-3-one 4-chloro-5-(2',5'-dichlorophenylsulfonyl)-1,2-dithiol-3-one 4-chloro-5- 3 -carboxyphenylsulfonyl l ,2-

dithiol-Z-one 4-chloro-5- (B-phenylethylsulfonyD-1,2-

dithio1-3-one 4-chloro-S-benzylsulfonyl-1,2-dithiol-3-one4-phenyl-5-methylsulfonyl-1,2-dithiol- 3-onel-chloro-1,2-dithiol-3-on-5-yl)-(A '-thiaz olin-2'-yl) sulfidebis(4-chloro-1,2-dithiol-3-on-5-yl) sulfide(4-chloro-1,2-dithiol-3-on-5-yl)-(A -imidazolin-2'-yl) sulfide(4-chloro-1,2-dithiol-3-on-5-yl)-(2'-chl0robenzyl) sulfoxide4,5-dichl0ro-1,2-dithiol-3-one (German patent application 1,102,174)4-phenyl-5-chloro-1,2-dithiol-3-one (German patent application1,126,668)

+ Q+ O C The action on bacteria was further ascertained by means of thefollowing bacteriostatic test on the following strains of bacteria:Staphylococcus aurcus SG 511, Escherichia coli, NCTC 8196, Bacilluspumilus.

The agar incorporation test according to Leonard and Blackford was usedas test method. Nutrient agar plates containing 100, 30, and 3 ppm. ofactive substance (ppm. means parts of active substance per 10 part ofdiluent) are inoculated with solutions of the above strains andincubated 2X 24 hours at 37. The marginal concentrations inhibiting thegrowth of the individual strains are given in the following table:

Bacil- Staph. E. coli la a aureus N OTC pumi- Compound 8 G 511 8196 Zu:

4-ehloro-fi-isopropylsullonyl-l,2-dithi01- 3 3O 3 -one.-chloro-fi-n-butylsulfonyl-L2-dithlol-3-one. 1O 3O 104-phenyl-5-methy1sulfonyl-1,ibdithiol-Z-one..- 3 3O 104chloro-5-ethy1sullonyl-1,2-dithiol-3-one 10 30 104-011loro-5-n-propylsullonyl-1,2-dithiol-3-oue. 10 30 104-chlore-5-(4-aminophenylsulfonyl)-1,2-

dtthiol-3-one 10 30 10 d-phenyl-fi-chlorod,2-dlthiol-3-one (Germanpatent application No. 1,126,668) 100 100 4-chloro-1,2-dithiol-3-onesubstituted in 5- position by:

Methylsulfinyl. 10 10 10 Ethylsulfinyl. 10 10 10 n-Propylsulfinyl 10 3010 2-cl1loroethylsulfinyl 10 30 10 Benzylsulfinyl 1 30 3Methoxy-carbonylmethylsultinyl. 10 10 102-imlno-3,1',3',44-thiadlezolinyl- 0 3 10 10 4-chlor0-2-dith1ol 5-0 3 103 Pyridyl-(2)-sulfinyl i 10 100 10 2-(acetoxy)-ethylth1o i. 10 100 10The fungicidal and bactericidal agents according to the invention areproduced in the known way by intimately mixing and milling activeingredients of Formula I with suitable carriers, optionally with theaddition of dispersing agents or solvents which are inert to the activesubstances. These agents can be made up into and used in the followingforms:

Solid forms: dust, scattering agents, granulates such as coatedgranules, impregnated granules, homogeneous granules;

Water dispersible concentrates of active substances: wettable powders,pastes, emulsions,

Liquid forms: solutions and aerosols.

To produce the solid forms for use (dusts, scattering agents,granulates), the active substances are mixed with solid carriers.Examples of carriers are kaolin, talcum, bole, loess, chalk, limestone,ground limestone, ataclay, dolomite, diatomaceous earth, precipitatedsilica, alkaline earth metal silicates, sodium and potassium aluminumsilicates (feldspar and mica), calcium and magnesium sulfates, magnesiumoxide, milled synthetic plastics, ferti-lisers such as ammonium sulfate,ammonium phosphates, ammonium nitrate, urea, ground vegetable productssuch as bran, bark dust, sawdust, ground nutshells, cellulose powder,residues of plant extractions, active charcoal, etc. These carriers canbe used alone or admixed with each other.

The particle size of the carriers is for dusts up to about 100;, forscattering agents from about 75,u-U.Z mm, and for granulates from 0.2-1mm. or coarser.

As a rule, the concentration of active substances in the solidpreparations is from about 05-30%.

To these mixtures can also be added additives which stabilize the activesubstance and/or nonionogenic, anionically and cationically activesubstances which, for example, improve the adhesion of the activesubstances on plants and parts of plants (glues and adhesives) and/ orattain better Wettability (wetting agents) and dispersibility(dispersing agents) of the active substances. Ex amples of adhesives areas follows: olein/chalk mixtures, cellulose derivatives (methylcelluloses, carboxymethyl celluloses), hydroxyethyl glycol ethers ofmonoand dialkyl phenols having 5-15 ethylene oxide radicals per moleculeand 8-9 carbon atoms in the alkyl radical, lignin sulfonic acids,alkaline and alkaline earth metal salts thereof, polyethylene glycolethers (Carbowaxes), fatty alcohol polyethylene glycol ethers having 5to 20 ethylene oxide radicals per molecule and 8-18 carbon atoms in thefatty alcohol moiety, condensation products of ethylene oxide/propyleneoxide, polyvinyl pyrrolidones, polyvinyl alcohols, condensation productsof urea-formaldehyde as well as Latex products.

The concentrates of active substance 'which can be dispersed in Water(wettable powders), pastes, and emulsion concentrates are agents whichcan be diluted with water to any concentration desired. They consist ofactive substance, carrier, optionally additives which stabilize theactive substance, surface active substances, and anti-foam agents and,optionally, solvents. The concentration of active substance in theseagents is 580%.

Wettable powders and pastes are obtained by mixing and milling theactive substances with dispersing agents and pulverulent carriers insuitable mixers and milling machines until homogeneity is attained.Carriers are, for example, those mentioned in the paragraph dealing withsolid forms for application. In some cases it is advantageous to usemixtures of different carriers. Examples of dispersing agents which canhe used are: condensation products of sulfonated naphthalene andsulfon-ated naphthalene derivatives and formaldehyde, condensationproducts of naphthalene or naphthalene sulfonic acids with phenol andformaldehyde as Well as alkali, ammonium and alkaline earth metal saltsor lignin sulfonic acid, further lalkylaryl sulfonates, alkali andalkaline earth metal salts of dibutyl naphthalene sulfonic acid, fattyalcohol sulfates such as salts of sulfated heXa dec-anols,heptadecanols, octadecanols, octadecenols and salts of sulfated fattyalcohol polyglycol ethers, the sodium salt of oleoyl ethionate, thesodium salt of oleoyl methyl tauride, ditert-iary acetylene glycols,dialkyl dilauryl ammonium chloride and fatty acid alkali and alkalineearth metal salts.

Silicones, Antifoam A, etc. are examples of antifoaming agents.

The active substances are so mixed, milled, sieved and strained with theadditives mentioned above that, in wettable powders, the solid particlesize of 2040,u. and, in pastes, of 3a, is not exceeded. To produceemulsion concentrates and pastes, dispersing agents such as those givenin the previous paragraphs, organic solvents and water are used.Examples of solvents are as follows: alcohols, benzene, xylenes,toluene, dimethyl sulfoxide and mineral oil fractions boiling between120 and 350. The solvents must be almost without smell, not phytotoxic,inert to the active substances, and not easily inflammable.

In addition, the agents according to the invention can be applied in theform of solutions. For this purpose the active substance or severalactive substances of Formula I are dissolved in suitable organicsolvents, mixtures of solvents or in water. Aliphatic and aromatichydrocarbons, chlorinated derivatives thereof, alkyl naphthalenes aloneor mixed with each other can be used as organic solvents. The solutionscontain the active substances in a concentration from 1 to 20%.

The agents described according to the invention can be mixed with otherbiocidally active compounds or agents. Thus, to broaden the range ofaction, the new agents can contain, e.g. insecticides, other fungicides,bac tericides, fungistatics, bacteriostatics or nematocides in additionto the compounds mentioned of Formula I. The agents according to theinvention can also contain fertilizers, trace elements, etc.

The following forms for application of the agents according to theinvention serve to illustrate the applicative aspect of the presentinvention; where not otherwise expressly stated, parts and percentagesare given by weight.

Dusts The following components are used to produce (a) a 10% and (b) a2% dust:

10 parts of l-chloro-1,2-dithiol-3-on-5-yl)-(benzy1)-sulphoxide,

5 parts of highly dispersed silica acid, and

85 parts of talcum,

2 parts of(4-chloro-l,2-dithiol-3-on-5-yl)-(methoxycarbonylmethyl)-sulphide, 1part of highly dispersed silica (e.g., Aerosil), and 97 parts of talcum.

To produce (0) a 10% and (d) a 2% dust, the following components areused:

10 parts of 4-chloro-5-phenylsulfonyl-1,2-dithiol-3-one, 5 parts ofhighly dispersed silica, and parts of talcum.

2 parts of 4-chloro-5-(2.'-5-dimethylphenylsulphonyl)-1,2-dithiol-3-one,

1 part of highly dispersed silica, and

97 parts of talcum.

The above active substances are intimately mixed and milled with thecarriers. The fungicidal dusts so obtained serve for the treatment ofseed beds or for the dusting of plants.

Seed dressings To produce (a) a 10% and (b) a 60% seed dressing, thefollowing are used:

10 parts of 4-chloro-S-methyls-ufonyl-1,2-dithiol-3-one, 5 parts ofkieselguhr 1 part of liquid parafiin 84 parts of talcum.

60 parts of 4-phenyl-S-methylsulfonyl-1,2-dithio1-3-one, 15 parts ofkieselguhr 1 part of liquid paraflin 24 parts of talcum.

The active substances mentioned are intimately mixed in a mixer with thecarriers given and the paratfin as distributing agent and then milled.The pulverulent seed dressings obtained serve for the treatment of seedsof all types.

Seed dressings of similar satisfactory properties are obtained byreplacing the active substance named in the compositions described under(a) and (b), supra, by the following active substances, respectively:

(a') S-(morpholino -thiocarbonyl-thio 4 chloro-l,2-di- 'thiol-3-one, (b)5-ethyl-sulfinyl-4-chloro-1,2-dithiol-3-one.

Granulates To produce (a) a 2.5% and (b) a 5% granulate, the followingcomponents are used:

2.5 parts of 4-phenyl-5-methylsulfonyl-l,2-dithiol-3-one, 2.5 parts ofkieselguhr 5 parts of polyethylene glycol 89.3 parts of ground limestone(0.4-0.8 mm. diameter) 0.7 part of silica.

5 parts of 4-ch1oro-5-n-butylsulfonyl-1,2-dithio1-3-one 1.5 parts ofkieselguhr 0.5 part of cetyl polyglycol ether 87 parts of groundlimestone 5 parts of polyethylene glycol 1 part of silica.

The ground limestone in each formulation is impregnated with thepolyethylene glycol or with the cetyl polyglycol ether and then mixedwith a mixture consisting of the active substance given, the silica andthe kieselguhr. These granulates are particularly suitable for thedisinfection of seed beds.

Granulates of similar satisfactory properties are obtained by replacingthe active substances used in the compositions described under (a) and(b), supra, by the following active substances, respectively:

Wettable powders To produce a 10% wettable powder, the followingcomponents are used:

10 parts of -4-chloro-S-chloromethylsulfonyl-1,2-dithiol-3- one 10 partsof sodium lignin sulfate 2 parts of a finely milled mixture of kaolinand polyvinyl alcohol (1: 1)

10 parts of kieselguhr 38 parts of kaolin 30 parts of Champagne chalk.

The active substance mentioned is mixed and finely milled with thecarriers and distributing agents. A wettable powder having excellentwettability and suspendibility is obtained. Suspensions of anyconcentration of active substance desired can be obtained from suchwettable powders by dilution with water. Such suspensions serve for thetreatment of cultivated plants and of materials and objects which aresubject to attack by fungi and bacteria.

A wettable powder of similar satisfactory properties is obtained byreplacing the active substance used in the composition described aboveby the following active substance:

5-isopropoxycarbonylmethyl-thio-4-chloro 1,2 dithiol- 3-one.

Emulsion concentrates To produce (a) and 5%, (b) a 10% and (c) a 15%emulsion concentrate, the following components are used:

5 parts of 4-chloro-S-phenylsulfonyl-1,2-dithiol-3-one 40 parts ofdimethyl formamide 50 parts of petroleum (boiling range 230-270") 5parts of a composite emulsifier consisting of the Ca salt ofdodecylbenzene sulfonic acid and a condensation product of ethyleneoxide and ricinus oil (e.g. Emullat WK, Union Chimique, S.A., Brussels).

10 parts of 4-(4'-tolyl)-5 methylsulfonyl-1,2-dithiol-3-one 35 parts ofdimethylformamide 50 parts of petroleum (boiling range 230-270) parts ofa composite emulsifier consisting of the Ca salt of dodecylbenzenesulfonic acid and a condensation product of ethylene oxide and ricinusoil (e.g. Emullat WK, Union Chimique, S.A., Brussels).

15 parts of 4-chloro-5-(fi-naphthylsulfonyD-l,2-dithiol-3- one 27 partsof dimethyl formamide 53 parts of petroleum (boiling range 230270) 5parts of a composite emulsifier consisting of the Ca salt ofdodecylbenzene sulfonic acid and a condensation product of ethyleneoxide and ricinus oil (e.g., Emullat WK, Union Chimique, S.A.,Brussels).

The active substance concerned is dissolved in petroleum or dimethylformamide and then the composite emulsifier is added to this solution.Emulsion concentrates are obtained which can be diluted with water toany concentration desired. Such emulsions are suitable for the treatmentof cultivated plants.

Emulsion concentrates of similar satisfactory properties are obtained byreplacing the active substance used in the compositions described under(a) to (0), supra, by the following active substances, respectively:

We claim: 1. A compound of the formula wherein Y represents 5, S0 or S0[R represents chlorine or phenyl optionally substituted by chlorine orlower alkyl,

R represents alkyl of from 1 to 6 carbon atoms, chloro lower alkyl;carboxyl lower alkyl; carbamoyl lower alkyl; N-lower alikylatedcarbamoyl lower alkyl; allrox carbonyl lower alkyl in which the alkoxymoiety has from 1 to 12 carbon atoms; lower alkanoyl lower alkyloptionally substituted in the alkanoyl moiety by chlorine; benzoyl loweralkyl; N-lower alkylated amino lower alkyl; lower alkyl sulphonyloxylower alkyl; lower allcoxy lower alkyl; lower alkanoylamino lower alkyl;phenyl, benzyl or phenethyl optionally substituted with one or moremembers selected from the group consisting of chlorine, bromine, alkylof from 1 to 9 carbon atoms, nitro, amino, dimethylamino, hydroxy,phenoxy, cyano, lower alkoxy, lower alkylthio, carboxy and loweralkoxycarbonyl; biphenyl; naphthyl; bromonaphthyl; naphthylmethyl; ortetrahydronaphthyl,

with the proviso that, when R represents phenyl or substituted phenyl, Rrepresents lower alkyl, phenyl or tolyl.

2. A compound according to claim 1 in which Y represents S, and Rrepresents chlorine.

3. A compound as defined in claim 2 which isS-(isopropoxycarbonyl-methylthio)-4-chloro-l,2-dithiol-3-one.

4. A compound as defined in claim 2 which is5-(methoxycarbonyl-methylthio)-4-chloro-1,2-dithiol-3-one.

5. A compound as defined in claim 2, which is 5-(2'-chloro-ethylthio)-4-chloro-1,2-dithiol-3-one.

6. A compound as defined in claim 2 which is 5-(2-methanesulfonyloxy-ethylthio)-4-chloro 1,2 dithiol-3- one.

7. A compound as defined in claim 2 which is 4-(chloro- 1,2-dithiol 3 on5 yl)-(dimethyl-carbamoyl-methyl)- sulphide.

8. A compound according to claim 1 in which Y represents S0 or S0 and Rrepresents chlorine.

9. A compound as defined in claim 8, which is 4-chloro-S-benzylsulfonyl-1,2-dithiol-3-one.

10. A compound as defined in claim 8, which isS-methylsulfinyl-4-chloro-1,2-dithiol-3-one.

11. A compound as defined in claim 8, which5-ethylsulfinyl-4-ch1oro-1,2-dithiol-3-one.

12. A compound as defined in claim 8, which isS-benzylsulfinyl-4-chloro-1,2-dithiol-3-one.

13. A compound as defined in claim 8, which is 5-(2'- chloro-benzyl-sulfinyl -4-chloro-1,2-dithiol-3 -one.

14. A compound as defined in claim 8, which is 5-(4'-methyl-benzyl-sulfinyl)-4-chloro-1,,2-dithiol-3-one.

15. A compound as defined in claim 12, which is (4-ch1oro 1,2dithiol-3-on-5-yl)-(2',4'-dimethylphenyl)- sulphoxide.

16. A compound according to claim 8 in which Y represents SO and Rrepresents lower alkyl, phenyl or phenyl substituted by lower alkyl.

31 32 17. A compound as defined in claim 16, which is 22. A compound asdefined in claim 12, which is4-chloro-5-methylsulfonyl-1,2-dithiol-3-one.S-(methyl-sulfonyl)-4-phenyl-1,2-dithiol-3-one.

18. A compound as defined in claim 16, which is 23. A compound asdefined in claim 21, which is 4-chloro-5-ethylsulfonyl-1,2-dithiol-3-one. 5- (ethyl-sulfonyl -4phenyl-1,2-dithiol-3-one.

19. A compound as defined in claim 16, which is 5 4-chloro-5-(4'-t0lylsul.fonyl) -1,2-dithiol-3-one. References Cited 20. A compoundas defined in claim 16, which is UNITED STATES PATENTS ignored-(2 ,4-d1methylphenylsu1fonyl) 1,2 d1th1ol-3- 3,546,235 12/1970 Bader et all260 294.8

21. A compound according to claim 1 in which Y rep- I resents S0 Rrepresents phenyl or phenyl substituted 10 HENRY HLES Pn mary Examinerby lower alkyl, and R represents lower al kyl. Assistant EXamlner

